Malonic esters, 2-halo-, reaction with

Oxidative cross-coupling reactions of alkylated derivatives of activated CH compounds, such as malonic esters, acetylacetone, cyanoacetates, and certain ketones, with nitroalkanes promoted by silver nitrate or iodine lead to the formation of the nitroalkylated products.67 This is an alternative way of performing SRN1 reactions using a-halo-nitroalkanes. 

Nucleophilic reactions at the carbon atoms of 1,3,4-thiadiazoles occur readily owing to the electron-deficient nature of this ring. Halo-substituted thiadiazoles are therefore highly activated and react with a wide range of nucleophiles. Carbon-based nucleophiles such as malonates have been used in the synthesis of 2-substituted thiadiazoles. When chlorothiadiazole 52 was treated with ethyl acetate in the presence of NaHMDS, the 2-phenyl-1,3,4-thiadiazol-5-ylacetic ester 53 was obtained (Equation 6) <20060L1447>. 

Dimethyl 3-(2-methyl-l-propenyl)-2,2-dimethylcyclopropane-l,l-dicarboxylate (324) is synthesized by the reaction of (2-halo-2-methylpropylidene)malonate (291) with 2-methyl-l-propenylmagnesium bromide (323). The cyclopropane is accompanied by the malonoester (325) and a butanolide (326) formed by nucleophilic attack of an ester enolate (equation 101) . ... 

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